Recording material employing chromogenic bisquinazolines

ABSTRACT

Chromogenic bisquinazolines of the formula ##STR1## wherein Q is the direct bond or an aliphatic or cycloaliphatic hydrocarbon radical, or is --CO--, --S-- or --SO 2  --, and 
     Y is the radical of a couplable compound, in particular an N-substituted 4-aminophenyl radical or a hydrogenated quinoline radical, and the rings A, B and D are unsubstituted or substituted by cyano, nitro, halogen, lower alkyl, phenyl, benzyl, lower alkoxy or lower alkoxycarbonyl. 
     These compounds are particularly suitable color formers for pressure-sensitive or heat-sensitive recording materials and produce intense yellow or orange colors of excellent fastness to light and, in particular, sublimation.

This is a continuation of application Ser. No. 542,226 filed on Oct. 14,1983, now U.S. Pat. No. 4,625,027.

The present invention relates to chromogenic bisquinazolines, to thepreparation thereof, and to the use of these compounds as colour formersin pressure-sensitive or heat-sensitive recording materials.

The novel bisquinazolines have the general formula ##STR2## wherein Q isthe direct bond, an aliphatic or cycloaliphatic hydrocarbon radicalcontaining not more than 8 carbon atoms, or is --CO--, --S-- or --SO₂--, and

Y is the radical of a couplable compound, and the rings

A, B und D may each independently be unsubstituted or substituted bycyano, nitro, halogen, lower alkyl, phenyl, benzyl, lower alkoxy orlower alkoxycarbonyl.

In the definition of the radicals of the bisquinazolines of thisinvention, lower alkyl and lower alkoxy normally denote those groups ormoieties of groups which contain 1 to 5, preferably 1 to 3, carbonatoms. Lower alkyl is e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, amyl or isoamyl, and lower alkoxy is e.g.methoxy, ethoxy, isopropoxy or tert-butoxy.

Q is preferably in the para-position with respect to both oxygen atoms.

Q as an aliphatic hydrocarbon radical is preferably an alkylene oralkylidene group. These groups may contain up to 8 carbon atoms and mayhave straight chain or branched chain configuration. The alkylene grouppreferably contains 1 to 4 carbon atoms and is e.g. the ##STR3## group.The alkylidene group is preferably ethylidene, propylidene,isopropylidene, butylidene or sec-butylidene. As a cycloaliphatichydrocarbon radical, Q is e.g. the cyclopentylene group, thecyclohexylene group, the cyclopentylidene group or, preferably, thecyclohexylidene group. These cycloaliphatic radicals may contain one ortwo methyl groups.

Q is preferably the aliphatic or cycloaliphatic radical, in particularmethylene or alkylidene of not more than 4 carbon atoms, and is mostpreferably isopropylidene, butylidene or cyclohexylidene.

Couplable compounds of which Y is a radical may be unsubstituted orN-mono-substituted or N,N-disubstituted anilines or naphthylamines,N-unsubstituted or N-substituted indoles, indolines, carbazoles,tetrahydrocarbazoles, dihydroquinolines, tetrahydroquinolines,dibenzylimides, benzomorpholines or phenylpyrazolines. Preferredcouplable compounds are N,N-disubstituted anilines or N-substitutedtetrahydroquinolines.

The monocyclic or polycyclic, carbocyclic or heterocyclic couplablecompounds may also contain one or more ring substituents. SuitableC-substituents are e.g. halogens, hydroxyl, cyano, nitro, lower alkyl,lower alkoxy, lower alkoxycarbonyl, C₁ -C₈ acyl, preferably loweralkylcarbonyl, alkylene, cycloalkyl, benzyl or phenyl, whilstN-substituents are preferably C₁ -C₁₂ alkyl, C₃ -C₁₂ alkenyl or benzyl,each of which may also be substituted by e.g. cyano, halogen, nitro,hydroxyl, lower alkyl, lower alkoxy or lower alkoxycarbonyl.

The alkyl and alkenyl radicals may have straight chain or branched chainconfiguration and are e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl,tert-butyl, sec-butyl, amyl, isoamyl, n-hexyl, 2-ethyl-hexyl, isooctyl,n-octyl, decyl or dodecyl, allyl, 2-methylallyl, 2-ethylallyl, 2-butenylor octenyl.

Acyl is preferably formyl, lower alkylcarbonyl, e.g. acetyl orpropionyl, or benzoyl. Further acyl radicals are lower alkylsulfonyl,e.g. methylsulfonyl or ethylsulfonyl, as well as phenylsulfonyl. Benzoyland phenylsulfonyl may be substituted by halogen, methyl, methoxy orethoxy.

The rings A, B and D are preferably not further substituted. If they docontain substituents, then each independently is substituted preferablyby halogen, lower alkyl or lower alkoxy, e.g. by chlorine, methyl,isopropyl, tert-butyl or methoxy. Each benzene ring can advantageouslycontain 1 or 2 substituents. Preferred substituents of the benzene ringsB and D are also methyl and tert-butyl as well as phenyl or benzyl.

Useful chromogenic bisquinazolines are those of the formula ##STR4##wherein A, B, D and Q have the meanings assigned to them and

Y₁ is an aminophenyl radical of the formula ##STR5## or a hydrogenatedheterocyclic radical of the formula ##STR6## wherein X₁ and X₂ are eachindependently hydrogen, C₁ -C₁₂ alkyl which is unsubstituted orsubstituted by halogen, hydroxyl, cyano or lower alkoxy, or arecycloalkyl, phenyl, benzyl, or phenyl or benzyl each substituted byhalogen, nitro, cyano, lower alkyl, lower alkoxy or lower alkoxycarbonylor

X₁ and X₂, together with the nitrogen atom to which they are attached,are a 5- or 6-membered, preferably saturated, heterocyclic radical,

X₃ is hydrogen, halogen, nitro, lower alkyl, lower alkoxy or loweralkoxycarbonyl, and

Z is hydrogen or C₁ -C₈ alkyl which is unsubstituted or substituted byhalogen, cyano or lower alkoxy, or is cycloalkyl or benzyl, and the ringE is unsubstituted or substituted by cyano, halogen, lower alkyl, e.g.methyl, or lower alkoxy such as methoxy, and the ring G is ahydrogenated 5- or 6-membered N-heterocyclic ring system which maycontain a further hetero atom as ring member, e.g. oxygen, sulfur ornitrogen, and which is unsubstituted or C-substituted by a member or,depending on the substituents, by more than one, especially two, of thesame or different members selected from halogen, cyano, hydroxyl, loweralkyl, lower alkoxy, C₅ -C₆ cycloalkyl, benzyl or C₃ -C₆ -alkylene.

Alkyl groups X₁ and X₂ may be straight chain or branched. Examples ofsuch alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, amyl, isoamyl, n-hexyl, 2-ethyl-hexyl, n-octyl, isooctyl orn-dodecyl.

X₁ and X₂ as substituted alkyl groups are in particular cyanoalkyl,haloalkyl, hydroxyalkyl or alkoxyalkyl, each containing preferably atotal of 2 to 4 carbon atoms, e.g. β-cyanoethyl, β-chloroethyl,β-hydroxyethyl, β-methoxyethyl, or β-ethoxyethyl.

X₁ and X₂ as cycloalkyl may be cyclopentyl or, preferably, cyclohexyl.

Preferred substituents of X₁ and X₂ as benzyl or phenyl are e.g. halogenatoms, cyano, methyl, methoxy or carbomethoxy. Examples of sucharaliphatic and aromatic radicals are methylbenzyl, chlorobenzyl,cyanophenyl, tolyl, chlorophenyl, methoxyphenyl or carbomethoxyphenyl.

A heterocyclic radical represented by X₁ and X₂, together with thenitrogen atom to which they are attached, is e.g. pyrrolidino,piperidino, pipecolino, morpholino, thiomorpholino or piperazino such asN-methylpiperazino. Preferred heterocyclic radicals --NX₁ X₂ arepyrrolidino, piperidino or morpholino.

Each of X₁ and X₂ independently is preferably lower alkyl, benzyl,phenyl, lower alkylphenyl or lower alkoxyphenyl. X₃ is preferablyhydrogen, chlorine, methyl, methoxy or ethoxy.

The ring E is preferably unsubstituted, but may with advantage contain amethyl group. The ring G is preferably 6-membered and C-substituted inparticular by 1, 2 or 3 methyl groups.

Z is preferably lower alkyl, benzyl or β-cyanoethyl.

Preferred bisquinazolines of the formula (2) are those in which Y₁ is aradical of the formula (2a).

Valuable chromogenic bisquinazolines are those of the formula ##STR7##wherein Q₁ is the direct bond, a straight chain or branched alkylene oralkylidene radical, each containing not more than 8, preferably not morethan 4, carbon atoms, or is the cyclohexylidene radical,

Y₂ is

an aminophenyl radical of the formula ##STR8## a 5-indoline radical ofthe formula ##STR9## a tetrahydroquinolinyl radical of the formula##STR10## a tetrahydroquinolinyl radical of the formula ##STR11## or abenzomorpholino radical of the formula ##STR12## in which formulae X₄and X₅ are each independently lower alkyl, cyano-lower alkyl, benzyl,phenyl, lower alkylphenyl or lower alkoxyphenyl, or

X₄ and X₅, together with the nitrogen atom to which they are attached,are pyrrolidino, piperidino or morpholino,

X₆ is hydrogen, halogen, lower alkyl or lower alkoxy,

Z₁ is hydrogen, C₁ -C₈ alkyl, C₂ -C₆ alkoxyalkyl, β-cyanoethyl orbenzyl,

T is hydrogen, halogen, lower alkyl, lower alkoxy, C₁ -C₄ acylamino orphenyl,

T₁ and T₂ are each hydrogen, halogen, hydroxy, lower alkyl or loweralkoxy, and

V₁, V₂, V₃ and V₄ are each hydrogen, lower alkyl, cycloalkyl or benzyl,or (V₁ and V₂) or (V₃ and V₄) are each together alkylene, and the ringsA₁, B₁ and D₁ are each independently unsubstituted or substituted by oneor two members of the group selected from cyano, halogen, lower alkyl,phenyl and lower alkoxy.

Preferred bisquinazolines of the formula (3) are those in which Y₂ is anaminophenyl radical of the formula (3a), wherein X₄ and X₅ are loweralkyl or benzyl. X₆ is preferably hydrogen. Q₁ is preferably in thepara-position to the O-atoms and is preferably C₁ -C₄ alkylene or C₂ -C₄alkylidene, in particular isopropylidene or butylidene. Q₁ is preferablyalso the cyclohexylidene radical. The ring A₁ is preferablyunsubstituted. The benzene rings B₁ and D₁ are preferably unsubstitutedor substituted by methyl and/or tert-butyl.

In the bisquinazolines of the formula (3), wherein Y₂ is a radical ofthe formula (3b), (3c), (3d) or (3e), the N-substituent Z₁ is preferablybenzyl, β-cyanoethyl or C₁ -C₈ alkyl, e.g. n-octyl, n-butyl, isopropylor, most preferably, methyl or ethyl. In these compounds of formula (3),Y₂ is preferably the tetrahydroquinolinyl radical of the formula (3d), Tis preferably hydrogen or methyl, T₁ is preferably hydrogen, methyl,hydroxyl or chlorine, T₂ is preferably hydrogen, methyl or ethyl, V₁ andV₂ are preferably hydrogen or methyl, and V₃ and V₄ are preferably eachlower alkyl and are most preferably each methyl.

Where (V₁ and V₂) or (V₃ and V₄) are each together alkylene, theypreferably contain 4 or 5 carbon atoms and, together with the linkingcarbon atom, form a cyclopentane or cyclohexane ring.

Very interesting bisquinazolines are those of the formula ##STR13## or,in particular, those of the formula ##STR14## wherein Q₂ is straightchain or branched alkylene or alkylidene each containing at most 4carbon atoms, or is cyclohexylidene,

X₇ and X₈ are each lower alkyl, β-cyanoethyl, benzyl or phenyl, or bothtogether with the nitrogen atom are piperidino,

X₉ is hydrogen, methyl, methoxy or ethoxy,

Z₂ is C₁ -C₈ alkyl, β-cyanoethyl or benzyl,

T₃, V₅ and V₆ are each lower alkyl, preferably methyl or ethyl,

T₄ is hydrogen or methyl, and

W is halogen, methyl, methoxy or preferably hydrogen, and the rings B₂and D₂ are unsubstituted or substituted by one or two substituentsselected from methyl, methoxy and tert-butyl.

The most preferred bisquinazolines are those of the formula (5), whereinQ₂ is butylidene or preferably isopropylidene. X₇ and X₈ are preferablybenzyl or, most preferably, lower alkyl.

Halogen in compounds containing the above substituents in formulae (1)to (5) is e.g. fluorine, bromine or preferably chlorine.

The bisquinzolines of the formula (1) are prepared by reacting 1 mole ofa bisphenol of the formula ##STR15## wherein B, D and Q have themeanings assigned to them, with 2 moles of a 4-haloquinazoline of theformula ##STR16## wherein A and Y have the meanings assigned to them andHal is halogen, e.g. bromine, fluorine or preferably chlorine.

The reaction of the compounds of formula (6) with the compound offormula (7) is conveniently carried out in the presence of an acidacceptor, e.g. an alkali metal hydroxide, an alkali metal carbonate or atertiary nitrogen base such as pyridine or a trialkylamine, andpreferably also in the presence of a quaternary ammonium salt, e.g.tetrabutylammonium bromide, optionally in an organic solvent or in anaqueous organic two-phase medium and at reflux temperature.

Examples of suitable solvents are: cycloaliphatic or aromatichydrocarbons, e.g. cyclohexane, benzene, toluene or xylene; chlorinatedhydrocarbons such as chloroform, ethylene chloride or chlorobenzenes;ethers such as diethyl ether or glycol dimethyl ether; cyclic etherssuch as dioxan or tetrahydrofuran; as well as dimethylformamide,diethylformamide, dimethylsulfoxide or acetonitrile.

Bisphenol compounds of the formula (6) which may be used as startingmaterials for the reaction with the quinzolines of the formula (7) aredescribed e.g. in U.S. Pat. No. 3 244 550.

Representative examples of bisphenols used as starting materials of theformula (6) are: 2,4'-methylenediphenol, 4,4'-methylenediphenol,2,2'-methylenediphenol, 4,4'-(1",1"-butylidene)diphenol,4,4'-sec-butylidenebiphenol, 4,4'-isopropylidenediphenol,4,4'-isopropylidene-bis(2-methylphenol), 4,4'-cyclopentylidenediphenol,4,4'-cyclohexylidenediphenol, 2,2'-methylene-di-p-cresol,4,4'-methylenedi-o-cresol,4,4'-methylene-bis(2-benzylphenol)-2,2'-methylene-bis(4-tert-butylphenol),2,2'-methylene-bis(4-tert-pentylphenol),2,2'-methylene-bis(4-chlorophenol), 4,4'-methylene-bis(2-chlorophenol),4,4'-(1"-methyl-n-hexylidene)diphenol,4,4'-(1",1"-butylidene)-bis(2-tert-butyl-5-methylphenol),2,2'-methylene-bis(4-phenylphenol), 4,4'-methylene-bis(2-phenylphenol),4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 2,2'-diphenol, 3,3'-diphenol,4,4'-diphenol, 4,4'-dihydroxybenzophenone or 2,2'-dihydroxybenzophenone.

The starting materials of the formula (7) can be obtained by oxidisinge.g. a 2-aminobenzamide of the formula ##STR17## with an aldehyde of theformula

    Y--CHO                                                     (9)

to give a 1,2,3,4-tetrahydroquinazol-4-one of the formula ##STR18##oxidising the compound of formula (10) to a compound of the formula##STR19## then replacing the hydroxyl group at the heterocyclic ring ofthe quinazoline system by a halogen atom, e.g. with phosphoroxy chloridein dichlorobenzene or with thionyl chloride in dimethylformamide, togive the starting compound of the formula (7). The 4-haloquinazoline soobtained can be further used without being isolated.

The oxidation of the reaction products of formula (10) to the4-quinazolones of the formula (11) is carried out with an oxidisingagent. Examples of suitable oxidising agents are chromates, bichromates,chlorates, chlorites, peroxides, e.g. hydrogen peroxide, manganesedioxide, lead dioxide, molecular oxygen, air, perborates, permanganates,nitrites, chlorine, bromine and, in particular, chloranil or bisulfites.

The best results with respect to yield and purity of the 4-quinazolonesare obtained with chloranil as oxidising agent.

Carrying out the oxidation with sodium bisulfite is advantageous fromthe environmental point of view. Quinzolones of the formula (11) areobtained in good purity and yield using this oxidising agent inaccordance with the method described in Synthesis 1981, (1), 35.

4-Haloquinazolines of the formula (7) and 4-quinazolones of the formula(11) and the preparation thereof are described e.g. in Europeanpublished patent application 33716.

The bisquinazolines of the formulae (1) to (5) are normally colourlessor, at most, faintly coloured. When these colour formers are broughtinto contact with a preferably acid developer, e.g. an electronacceptor, they produce intense yellow or orange shades of excellentfastness to sublimation and light. They are therefore also very usefulwhen mixed with one or more other known colour formers, for example3,3-(bis-aminophenyl)phthalides, 3-indolyl-3-aminophenylazaphthalides,3,3-(bis-indolyl)phthalides, 3-aminofluoranes, 2,6-diaminofluoranes,leucoauramines, spiropyranes, spirodipyranes, chromenoidoles,phenoxazines, phenothiazines, carbazolylmethanes or othertriarylmethaneleuco dyes, to give blue, grey or black colorations.

The bisquinazolines of the formulae (1) to (5) exhibit both on phenolicsubstrates, and especially on activated clays, an excellent colourintensity and fastness to sublimation and light. They are suitable inparticular as rapidly developing colour formers for use in aheat-sensitive or especially in a pressure-sensitive recording materialwhich can also be a copying material.

A pressure-sensitive material consists, for example, of at least onepair of sheets which contain at least one colour former of the formulae(1) to (5) dissolved in an orgaic solvent, and a solid electron acceptoras developer.

Typical examples of such developers are activated clays such asattapulgite, acid clay, bentonite, montmorillonite, activated clay, e.g.acid-activated bentonite or montmorillonite, and also zeolith,halloysite, silica, alumina, aluminium sulfate, aluminium phosphate,zinc chloride, activated kaolin or any clay. Preferred developers areacidic organic compounds, for example unsubstituted or ring-substitutedphenols, salicylic acid or salicylates and their metal salts, or anacidic polymer, for example a phenolic polymer, an alkylphenolacetyleneresin, a maleic acid/rosin resin or a partially or completely hydrolysedpolymer of maleic acid and styrene, ethylene or vinyl methyl ether, orcarboxypolymethylene. Mixtures of these polymers can also be used.Particularly preferred developers are acid clays, zinc salicylates orthe condensation products of p-substituted phenols with formaldehyde.These latter may also contain zinc.

The developers may also be used in admixture with other basically inertor almost inert pigments, or with other auxiliaries such as silica gelor UB absorbers such as 2-(2-hydroxyphenyl)benzotriazoles. Examples ofsuch pigments are: talcum, titanium dioxide, zinc oxide, chalk, clayssuch as kaolin, as well as organic pigments, e.g. urea/formaldehydecondensates (BET surface area of 2-75 g/m²) or melamine/formaldehydecondensates.

The colour former effects a coloured marking at those points where itcomes into contact with the electron acceptor. In order to prevent thecolour formers contained in the pressure-sensitive recording materialfrom becoming active prematurely, they are usually separated from theelectron acceptor. This separation can conveniently be accomplished byincorporating the colour formers in foamlike, spongelike orhoneycomb-like structures. The colour formers are preferablyencapsulated in microcapsules, which as a rule can be ruptured bypressure.

When the capsules are ruptured by pressure, for example with a pencil,the colour former solution is transferred to an adjacent sheet which iscoated with an electron acceptor and a coloured area is thus produced.This colour results from the dye which is formed and which is absorbedin the visible range of the electromagnetic spectrum.

The colour formers are encapsulated preferably in the form of solutionsin organic solvents. Examples of suitable solvents are preferablynon-volatile solvents, for example a polyhalogenated paraffin, such aschloroparaffin, or a polyhalogenated diphenyl, such asmonochlorodiphenyl or trichlorodiphenyl, and also tricresyl phosphate,di-n-butyl phthalate, dioctyl phthalate, trichlorobenzene,trichloroethylphosphate, an aromatic ether such as benzylphenyl ether, ahydrocarbon oil such as paraffin or kerosene, an alkylated (e.g. withisopropyl, isobutyl, sec- or tert-butyl) derivative of diphenyl,naphthalene or triphenyl; dibenzyl toluene, terphenyl, partiallyhydrogenated terphenyl, a benzylated xylene, a mono- or tetramethylateddiphenylalkane or other chlorinated or hydrogenated, condensed aromatichydrocarbons. Mixtures of different solvents, especially mixtures ofparaffin oils or kerosene and diisopropylnaphthalene or partiallyhydrogenated terphenyl, are often used in order to obtain an optimumsolubility for the colour formation, a rapid and intense coloration, anda viscosity which is advantageous for the microencapsulation.

The capsule walls can be formed evenly around the droplets of the colourformer solution by coacervation; and the encapsulating material canconsist of gelatin and gum arabic, as described e.g. in U.S. Pat. No.2,800,457. The capsules can also be formed preferably from an aminoplastor a modified aminoplast by polycondensation, as described in Britishpatent specifications Nos. 989 264, 1 156 725, 1 301 052 and 1 355 124.Also suitable are microcapsules which are formed by interfacialpolymerisation, e.g. capsules formed from polyester, polycarbonate,polysulfonamide, polysulfonate, but in particular from polyamide orpolyurethane.

The microcapsules containing the colour formers of the formulae (1) to(5) can be used for the production of a wide variety of known kinds ofpressure-sensitive copying material. The various systems differsubstantially from one another in the arrangement of the capsules, ofthe colour reactants, i.e. the developers, and/or of the support. Apreferred arrangement is that in which the encapsulated colour former isin the form of a layer on the back of a transfer sheet and the developeris in the form of a layer on the face of a receiver sheet.

Another arrangement of the components is that wherein the microcapsuleswhich contain the colour former, and the developer, are in or on thesame sheet, in the form of one or more individual layers, or are presentin the paper pulp.

The capsules are preferably secured to the support by means of asuitable adhesive. As paper is the preferred support, these adhesivesare principally paper-coating agents, for example gum arabic, polyvinylalcohol, hydroxymethyl cellulose, casein, methyl cellulose, dextrin,starch or starch derivatives or polymer latices. These latter are e.g.butadiene/styrene copolymers or acrylic homopolymers or copolymers.

The paper employed comprises not only normal paper made from cellulosefibers, but also paper in which the cellulose fibres are replaced(partially or completely) by synthetic polymers.

The compounds of the formulae (1) to (5) can also be employed as colourformers in a thermoreactive recording material. This recording materialusually contains at least one carrier, one colour former, one electronacceptor and, optionally, also a binder. Thermoreactive recordingsystems comprise, for example, heat-sensitive recording or copyingmaterials or papers. These systems are used e.g. for recordinginformation, for example in electronic computers, teleprinters ortelewriters, or in recording and measuring instruments, e.g.electrocardiographs. The image (mark) formation can also be effectedmanually with a heated pen. Laser beams can also be used to produceheatinduced marks.

The thermoreactive recording material can be composed such that thecolour former is dispersed or dissolved in one binder layer and thedeveloper is dissolved or dispersed in the binder in a second layer.

Another possibility consists in dispersing both the colour former andthe developer in one layer. Be means of heat the binder is softened atspecific areas and the colour former comes into contact with thedeveloper (electron acceptor) at those points where heat is applied andthe desired colour develops at once.

Suitable developers are the same electron acceptors as are used inpressure-sensitive papers. Examples of developers are the clays alreadymentioned and especially phenolic resins, or also the phenolic compoundsdescribed e.g. in German Offenlegungsschrift No. 1 251 348, for example4-tert-butylphenyl, 4-phenylphenol, 4-hydroxydiphenyl ether, α-naphtol,β-naphthol, 4-hydroxymethylbenzoate, 4-hydroxyacetophenone,2,2'-dihydroxydiphenyl, 4,4-isopropylidenediphenol,4,4'-isopropylidene-bis(2-methylphenol), 4,4'-bis(hydroxyphenyl)valericacid, 2,2'-methylene-bis(4-phenylphenol), hydroquinone, pyrogallol,phloroglucinol, p-, m- and o-hydroxybenzoic acid, gallic acid,1-hydroxy-2-naphthoic acid, as well as boric acid or organic, preferablyaliphatic, dicarboxylic acids, for example tartaric acid, oxylic acid,maleic acid, citric acid, citraconic acid or succinic acid.

Fusible, film-forming binders are preferably used for the manufacture ofthe thermoreactive recording material. These binders are normallywater-soluble, whereas the bisquinazolines and the developer aresparingly soluble or insoluble in water. The binder should be able todisperse and fix the colour former and the developer at roomtemperature.

By applying heat the binder softens or melts, so that the colour formercomes in contact with the developer and a colour is able to form.Examples of binders which are soluble, or at least swellable, in waterare e.g. hydrophilic polymers, for example polyvinyl alcohol,polyacrylic acid, hydroxyethylcellulose, methyl cellulose,carboxymethylcellulose, polyacrylamide, polyvinyl pyrrolidone, gelatinor starch.

If the colour former and the developer are in two separate layers, it ispossible to use water-insoluble binders, i.e. binder which are solublein non-polar or only weakly polar solvents, for example natural rubber,synthetic rubber, chlorinated rubber, alkyd resins, polystyrene,styrene/butadiene copolymers, polymethylacrylates, ethyl cellulose,nitrocellulose and polyvinyl carbazole. The preferred arrangement,however, is that in which the colour former and the developer arecontained in one layer in a water-soluble binder.

The thermoreactive coatings may contain further ingredients. To improvethe degree of whiteness, to facilitate the printing of papers, and toprevent the heated pen from sticking, the coatings may contain e.g.talcum, titanium dioxide, zinc oxide, aluminium hydroxide, calciumcarbonate (e.g. chalk), clays or also organic pigments, for exampleurea/formaldehyde polymers. In order to effect the colour formation onlywithin a limited temperature range, it is possible to add substancessuch as urea, thiourea, diphenyl thiourea, acetamide, acetanilide,stearyl amide, phthalic anhydride, metal stearates, phthalonitrile orother appropriate fusible products which induce the simultaneous meltingof the colour former and the developer. Thermographic recordingmaterials preferably contain waxes, e.g. carnauba wax, montan wax,paraffin wax or polyethylene wax.

The invention is illustrated by the following Examples, in whichpercentages are by weight, unless otherwise indicated.

EXAMPLE 1

26.5 g of the quinazolone of the formula ##STR20## are dissolved in 150g of 1,2-dichlorobenzene at 150° C. The solution is then cooled to 90°C. and 15.3 g of phosphoroxy chloride are added dropwise at 90°-95° C.over 1/2 hour. The reaction mixture is stirred for 1 hour at thistemperatuure to give a dark red solution of the4-chloro-2-(4'-dimethylaminophenyl)quinazoline of the formula ##STR21##This solution is poured into a suspension of 11.4 g of4,4'-isopropylidenediphenol (bisphenol A) and 2 g of tetrabutylammoniumbromide in 64 g of 50% sodium hydroxide solution over the course of 1/2hour. The reaction mixture is then refluxed for 1 hour, after which thedichlorobenzene is removed by steam distillation. The productprecipitates in crystals, which are isolated by filtration at 50° C.,washed with water and methanol and dried in vacuo at 80° C., affording33.1 g of a bisquinazoline of the formula ##STR22## with a melting pointof 204°-206° C.

The reflectance maximum of this bisquinazoline on paper coated with acidclay is in the range of 465 nm.

This colour former develops a yellow colour of excellent fastness oflight and sublimation on acid clay.

EXAMPLE 2

The quinazolone of the formula (i) in Example 1 is replaced by 29.3 g ofthe quinazolone of the formula ##STR23## and the same procedure isrepeated, affording 34.2 g of a bisquinazoline of the formula ##STR24##A sample recrystallised from toluene/methanol melts at 147°-150° C. Thereflectance maximum on paper coated with acid clay is in the range of470 nm.

This colour former develops a yellow colour of excellent fastness tolight and sublimation on acid clay.

EXAMPLE 3

The isopropylidene compound employed in Example 1 is replaced by 19.2 gof a bisphenol compound of the formula ##STR25## and the same procedureis repeated, affording 17.2 g of a bisquinazoline compound of theformula ##STR26## with a melting point of 145°-160° C.

The reflectance maximum on paper coated with acid clay is in the rangeof 465 nm.

This colour former develops a yellow colour of excellent fastness tolight and sublimation on paper coated with acid clay.

The bisquinazolines of the formula (24) ##STR27## listed in thefollowing table are obtained in the same manner as described in Examples1 to 3, using the corresponding starting materials.

                                      TABLE                                       __________________________________________________________________________                                      Colour                                      Example                                                                            T'              Q.sub.3 m.p./°C.                                                                    acid clay                                   __________________________________________________________________________          ##STR28##      isopropylidene                                                                        60-70                                                                              yellow                                      5                                                                                   ##STR29##      isopropylidene                                                                        130-135                                                                            yellow                                      6                                                                                   ##STR30##      isopropylidene                                                                        119-123                                                                            yellow                                      7    N(n-C.sub.3 H.sub.7).sub.2                                                                    isopropylidene                                                                        100-105                                                                            yellow                                      8                                                                                   ##STR31##      isopropylidene                                                                        70-80                                                                              yellow                                      9    N(CH.sub.3).sub.2                                                                             CH.sub.2                                                                              209-220                                                                            yellow                                      10   N(CH.sub.3).sub.2                                                                             cyclohexylidene                                                                       216-225                                                                            yellow                                      11                                                                                  ##STR32##      isopropylidene                                                                        155-170                                                                            yellow                                      __________________________________________________________________________

EXAMPLE 12

19 g of the quinazolone of the formula ##STR33## are dissolved at 150°C. in 90 g of 1,2-dichlorobenzene. The solution is then cooled to 95° C.and 9 g of phosphoroxy chloride are added dropwise at this temperatureover 30 minutes. The reaction mixture is then stirred for 1 hour at90°-95° C. The red solution of the4-chloro-2-tetrahydroquinolinylquinazoline of the formula ##STR34## ispoured over the course of 15 minutes into a suspension consisting of11.4 g of 4,4'-isopropylidenediphenol, 2.2 g of tetrabutylammoniumbromide and 35 g of a 50% aqueous solution of sodium hydroxide,whereupon the temperature rises to 110° C. The reaction mixture isstirred for 1 hour at 100°-110° C. and the 1,2-dichlorobenzene isremoved by steam distillation. The precipitated product is dissolved intoluene with heating and the hot toluene solution is filtered overactivated carbon. The product crystallises on cooling and the crystalsare isolated by filtration and dried, affording 12 g of a compound ofthe formula ##STR35## with a melting point of 193°-196° C.

This colour former develops a golden yellow colour of good fastness tolight and sublimation on acid clay.

The quinazolone of the formula (iv) employed in Example 12 is preparedas follows:

23.1 g of N-ethyl-2,2,4-trimethyl-tetrahydroquinoline-6-aldehyde aredissolved in 150 ml of ethanol. To this solution are added 13.6 g ofanthranilamide and 4 ml of 10% sulfuric acid and the reaction mixture isheated to 60° C. The mixture is kept for 1 hour at 60° C. and theproduct is oxidised by the dropwise addition of 69 g of a 40% aqueoussolution of sodium bisulfite and then stirring the reaction mixture for2 hours at reflux temperature. After cooling to room temperature, theprecipitated product is isolated by filtration, washed with ethanol anddried, affording 19 g of the quinazolone of the formula (iv) with amelting point of 215°-219° C.

EXAMPLE 13 Preparation of a pressure-sensitive copying paper

A solution of 3 g of the bisquinazoline of the formula (21) in 80 g ofdiisopropylnaphthalene and 17 g of kerosene are microencapsulated bycoacervation in a manner known per se with gelatin and gum arabic. Themicrocapsules are mixed with starch solution and coated on a sheet ofpaper. The face of a second sheet of paper is coated with acid-activatedbentonite as colour developer. The first sheet and the sheet coated withthe developer are laid on top of each other with the coated sides faceto face. Pressure is exerted on the first sheet by writing by hand ortypewriter and an intense yellow copy of excellent lightfastnessdevelops immediately on the sheet coated with the developer.

Corresponding intense yellow copies which are fast to sublimation andlight are also obtained using each of the other colour formers of theformulae (22) to (25) as indicated in the Preparatory Examples.

EXAMPLE 14 The procedure of Example 13 is repeated, replacing thebisquinazoline of the formula (21) by a mixture of the followingcomposition: 1.2 g of3,3-bis-(4'-dimethylaminophenyl)-6-dimethylaminophthalide, 1.2 g ofN-butylcarbazol-3-yl-bis-(4'-N-methyl-N-phenylaminophenyl)methane, 1.5 gof the bisquinazoline of the formula (21) and 0.4 g of3,3-bis-(N-n-octyl-2'-methylindol-3'-yl)phthalide. The so obtainedpressure-sensitive recording material gives an intense and lightfastblack copy when pressure is exerted by hand or typewriter. EXAMPLE 15

1 g of the bisquinazoline of the formula (22) is dissolved in 17 g oftoluene. With stirring, 12 g of polyvinyl acetate, 8 g of calciumcarbonate and 2 g of titanium dioxide are added to this solution. Theresultant suspension is diluted with toluene in the weight ratio 1:1 andcoated on a sheet of paper with a knife to a thickness of 10 μm. On thissheet of paper is laid a second sheet, the underside of which has beencoated to a weight of 3 g/m² with a mixture consisting of 1 part of anamide wax, 1 part of a stearin wax and 1 part of zinc chloride. Pressureis exerted on the top sheet by hand or typewriter and an intense yellowcolour which is fast to sublimation and light develops immediately onthe sheet coated with the colour former.

EXAMPLE 16 Preparation of a heat-sensitive recording material

In a ball mill, 32 g of 4,4'-isopropylidenediphenol (bisphenol A), 3.8 gof the distearylamide of ethylenediamine, 38 g of kaolin, 20 g of an 88%hydrolysed polyvinyl alcohol and 500 ml of water are ground to particlesize of about 5 μm. In a second ball mill, 6 g of the bisquinazoline ofthe formula (21), 3 g of an 88% hydrolysed polyvinyl alcohol and 60 mlof water are ground to particle size of about 3 μm.

Both dispersions are mixed and coated on paper to a dry coating weightof 5.5 g/m². An intense yellow colour of excellent fastness to light andsublimation is produced by contacting the paper with a heated ballpointpen. Intense and lightfast yellow colours can also be obtained usingeach of the other colour formers of the formulae (22) to (25).

EXAMPLE 17

In a ball mill, 2.7 g of the bisquinazoline of the formula (22), 24 g ofN-phenyl-N'-(1-hydroxy-2,2,2-trichloroethyl)-urea, 16 g of stearylamide,59 g of an 88% hydrolysed polyvinyl alcohol and 58 ml of water areground to a particle size of 2-5 μm. This suspension is coated on asheet of paper to a dry coating weight of 5.5 g/m². An intense yellowwhich is fast to sublimation and light is obtained by contacting thepaper with a heated ball-point pen.

What is claimed is:
 1. A pressure sensitive or heat-sensitive recordingmaterial which comprises a support which contains, or has coatedthereon, as a color former, at least one bisquinazoline of the formula##STR36## wherein Q is the direct bond, an aliphatic or cycloaliphatichydrocarbon radical containing not more than 8 carbon atoms, or is--CO--, --S-- or --SO₂ --, andY is the radical of a couplable compoundselected from the group consisting of unsubstituted or N-monosubstitutedor N,N-disubstituted anilines or naphthylamines, N-unsubstituted orN-substituted indoles, indolines, carbazoles, tetrahydrocarbazoles,dihydroquinolines, tetrahydroquinolines, dibenzylimides,benzomorpholines or phenylpyrazolines, and the rings A, B and D eachindependently are unsubstituted or substituted by cyano, nitro, halogen,lower alkyl, phenyl, benzyl, lower alkoxy or lower alkoxycarbonyl.
 2. Arecording material according to claim 1 whereinY is a radical of theformula ##STR37## or the radical of the formula ##STR38## wherein X₁ andX₂ are each independently hydrogen, C₁ -C₁₂ alkyl which is unsubstitutedor substituted by halogen, hydroxy, cyano or lower alkoxy, or arecycloalkyl, phenyl, benzyl, or phenyl or benzyl each substituted byhalogen, nitro, cyano, lower alkyl, lower alkoxy or lower alkoxycarbonylorX₁ and X₂, together with the nitrogen atom to which they are attached,are a 5- or 6-membered heterocyclic radical, X₃ is hydrogen, halogen,nitro, lower alkyl, lower alkoxy or lower alkoxycarbonyl, and Z ishydrogen or C₁ -C₈ alkyl which is unsubstituted or substituted byhalogen, cyano or lower alkoxy, or is cycloalkyl or benzyl, and the ringE is unsubstituted or substituted by cyano, halogen, lower alkyl orlower alkoxy, and the ring G is a hydrogenated 5- or 6-memberedN-heterocyclic ring system which is unsubstituted or C-substituted byone or more than one of the same or different substituents selected fromthe group consisting of halogen, cyano, hydroxyl, lower alkyl, loweralkoxy, C₅ -C₆ cycloalkyl, benzyl or C₃ -C₆ alkylene.
 3. A recordingmaterial according to claim 2 wherein Y is a radical of the formula(2a).
 4. A recording material according to claim 3 wherein X₁ and X₂ areeach independently lower alkyl, benzyl, phenyl, lower alkylphenyl orlower alkoxyphenyl.
 5. A recording material according to claim 2 whereinY is a radical of the formula (2b) and ring G is a 6-memberedN-heterocyclic ring system.
 6. A recording material according to claim 2wherein Y is a radical of the formula (2b) and Z is lower alkyl, benzyl,or beta-cyanoethyl.
 7. A recording material according to claim 1 whereinQ is an aliphatic hydrocarbon radical containing up to 8 carbon atoms ora cycloaliphatic hydrocarbon radical containing 5-7 carbon atoms in thering which may contain one or two methyl groups on the ring.
 8. Arecording material according to claim 1, wherein Q is bonded to rings Band D in the para position on each with respect to the oxygen atoms. 9.A pressure-sensitive or heat-sensitive recording material whichcomprises a support which contains, or has coated thereon, as a colorformer, at least one bisquinazoline of the formula ##STR39## wherein Q₁is the direct bond, a straight chain or branched alkylene or alkylideneradical, each containing not more than 8 carbon atoms, or is acyclohexylidene radical,Y₂ isan aminophenyl radical of the formula##STR40## a 5-indoline radical of the formula ##STR41## atetrahydroquinolinyl radical of the formula ##STR42## atetrahydroquinolinyl radical of the formula ##STR43## or abenzomorpholino radical of the formula ##STR44## in which formulae X₄and X₅ are each independently lower alkyl, cyano-lower alkyl, benzyl,phenyl, lower alkylphenyl or lower alkoxyphenyl, orX₄ and X₅, togetherwith the nitrogen atom to which they are attached, are pyrrolidino,piperidino or morpholino, X₆ is hydrogen, halogen, lower alkyl or loweralkoxy, Z₁ is hydrogen, C₁ -C₈ alkyl, C₂ -C₆ alkoxyalkyl, β-cyanoethylor benzyl, T is hydrogen, halogen, lower alkyl, lower alkoxy, C₁ -C₄acylamino or phenyl, T₁ and T₂ are each hydrogen, halogen, hydroxy,lower alkyl or lower alkoxy, and V₁, V₂, V₃ and V₄ are each hydrogen,lower alkyl, cycloalkyl or benzyl, or (V₁ and V₂) or (V₃ and V₄) areeach together alkylene, and the rings A₁, B₁ and D₁ are eachindependently unsubstituted or substituted by one or two members of thegroup selected from cyano, halogen, lower alkyl, phenyl and loweralkoxy.
 10. A recording material according to claim 9 wherein Y₂ is aradical of the formula (3a).
 11. A recording material according to claim10 wherein X₄ and X₅ are each lower alkyl or benzyl and X₆ is hydrogen.12. A recording material according to claim 9 wherein Q₁ is C₁ -C₄-alkylene or C₂ -C₄ -alkylidene.
 13. A recording material according toclaim 9 wherein ring A₁ is unsubstituted and rings B₁ and D₁ areunsubstituted or substituted by one or two substituents selected frommethyl and tert.-butyl.
 14. A recording material according to claim 9wherein Y₂ is a radical of formula (3d).
 15. A recording materialaccording to claim 9 wherein Y₂ is a radical of formula (3e).
 16. Arecording material according to claim 15 wherein Z₁ is benzyl,beta-cyanoethyl or C₁ -C₈ -alkyl.
 17. The pressure-sensitive recordingmaterial of claim 9 wherein the bisquinazoline is dissolved in anorganic solvent, and which recording material further comprises at leastone solid electron acceptor.
 18. The pressure-sensitive recordingmaterial of claim 17, wherein the bisquinazoline is encapsulated inmicrocapsules.
 19. The pressure-sensitive recording material of claim18, wherein the encapsulated bisquinazoline is present in the form of alayer on the back of transfer and the electron acceptor is present inthe form of a layer on the face of a receiver sheet.
 20. Thepressure-sensitive recording material of claim 9, which comprises thebisquinazoline together with one or more other color formers.
 21. Theheat-sensitive recording material of claim 9, which comprises in atleast one layer, at least one bisquinazoline color former, at least oneelectron acceptor and at least one binder.
 22. A pressure-sensitive orheat-sensitive recording material which comprises a support whichcontains, or has coated thereon, as a color former, at least onebisquinazoline of the formula ##STR45## wherein Q₂ is straight chain orbranched alkylene or alkylidene each of at most 4 carbon atoms, orcyclohexylidene,X₇ and X₈ are each lower alkyl, β-cyanoethyl, benzyl orphenyl, or --NX₇ X₈ is piperidino, X₉ is hydrogen, methyl, methoxy orethoxy, W is hydrogen, halogen, methyl or methoxy and the rings B₂ andD₂ are unsubstituted by one or two substituents selected from methyl,methoxy and tert-butyl.
 23. A recording material according to claim 22wherein each of the rings B₂ and D₂ is unsubstituted or substituted bymethyl or tert-butyl.
 24. A pressure-sensitive or heat-sensitiverecording material which comprises a support which contains, or hascoated thereon, as a color former, at least one bisquinazoline of theformula ##STR46## wherein Q₂ is straight chain or branched alkylene oralkylidene each containing at most 4 carbon atoms,Z₂ is C₄ -C₈ alkyl,β-cyanoethyl or benzyl, T₃, V₅ and V₆ are each lower alkyl, T₄ ishydrogen or methyl, and W is hydrogen, halogen, methyl or methoxy, andthe rings B₂ and D₂ are unsubstituted or substituted by one or twosubstituents selected from methyl, methoxy and tert-butyl.